Acceleration of Long‐Range Photoinduced Electron Transfer through DNA by Hydroxyquinolines as Artificial Base Pairs

Bätzner, Effi; Liang, Yujun; Schweigert, Caroline; Unterreiner, Andreas‐Neil; Wagenknecht, Hans‐Achim

doi:10.1002/cphc.201500062

Cited by 9 publications

(8 citation statements)

References 39 publications

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“…A photoexcitable dimethylaminopyrenyl donor attached to a deoxyuracil ( AP dU, E red *=−2.2 V vs. NHE) that exhibits suitable redox properties for long range charge transfer experiments was successfully used by Bätzner et al. to inject an electron in hydroquinoline base surrogates …”

Section: Figurementioning

confidence: 99%

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Modulation of Excess Electron Transfer through LUMO Gradients in DNA Containing Phenanthrenyl Base Surrogates

Roethlisberger

Kaliginedi

Leumann

2017

Chemistry A European J

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The modulation of excess electron transfer (EET) within DNA containing a dimethylaminopyrene (C-AP) as an electron donor and 5-bromouracil ( Br dU) as a electron acceptor through phenanthrenyl pairs (phen-R) could be achieved by modifying the phenanthrenyl base surrogates with electron withdrawing and donating groups. Arranging the phenanthrenyl units to form a descending LUMO gradient increased the EET efficiency compared to the electron transfer through uniform LUMOs or an ascending LUMO gradient.The well-defined double helical structure of DNA with the linear arranged base pairs represents a suitable scaffold for charge transfer and is therefore subject to intense studies in DNA damage, [1] sensors [2] and applications in molecular electronics.[3]The reductive electron transfer also called excess electron transfer (EET) in DNA is a process that is directed through the lowest unoccupied molecular orbital (LUMO) of the DNA bases. Investigations elucidated that the charge transfer over longer distances occurs via electron hopping mostly through thymine bases (k = 10 10 s -1). [4] In earlier studies it was shown that the replacement of the natural base pairs by non-hydrogen bonding base surrogates with extended aromatic surfaces such as phenanthrene could have beneficial conducting properties and could overcome the physico-chemical limitations of the natural nucleobases.[5] Regarding the reduction of such base surrogates the choice of the electron injector is crucial for the success of the experiments. Investigations by Grigorenko et. al. revealed that pyrene ( Py dU, Ered* = -2.2 V vs NHE) [6] only enables a superexchange mechanism, whereas phenothiazine (PTZ, Ered* = -2.7 V vs SCE) [7] allowed to trigger the system into an electron hopping mechanism with a transport that spreads over longer distances.[5] A photoexcitable dimethyl amino-pyrenyl donor attached to a deoxyuracil ( AP dU, Ered* = -2.2 V vs NHE) [8] that exhibits suitable redox properties for long range charge transfer experiments was successfully used by Bätzner et. al. to inject an electron in hydroquinoline base surrogates. [9] In this study, we investigated the EET through DNA containing phenanthrenyl base surrogates with different reduction potentials and LUMO energy levels. It is believed that the electron transfer within DNA can be modulated by the installation of a potential energy gradient.[10] The predicted advantage of such a redox/LUMO gradient was envisioned to be the unidirectionality of the electron transfer and therefore a gain in efficiency. The installation of the different reduction potentials was deemed to be possible by the introduction of electron withdrawing (CN) and donating (NH2) groups at the 7-position of the phenanthrene (phen). The synthesis of the NH2 phen and phen phosphoramidites applicable for automated DNA synthesis was performed according to published procedures.[11] The introduction of a cyano group required a palladium catalyzed substitution of the intermediate 9 with copper-(I)-cyanide. Tritiylation and phosphiti...

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Section: Figurementioning

confidence: 99%

“…to inject an electron in hydroquinoline base surrogates. [9] In this study, we investigated the EET through DNA containing phenanthrenyl base surrogates with different reduction potentials and LUMO energy levels. It is believed that the electron transfer within DNA can be modulated by the installation of a potential energy gradient.…”

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confidence: 99%

Modulation of Excess Electron Transfer through LUMO Gradients in DNA Containing Phenanthrenyl Base Surrogates

Roethlisberger

Kaliginedi

Leumann

2017

Chemistry A European J

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“…The structural stability of double helical DNA is primarily due π-electron stacking interactions between adjacent base pairs. It is this π-system that enables electron transfer (ET) throughout DNA [ 55 , 56 , 57 , 58 ]. Electrons migrate across charge carrying bases in a multistep hopping process, where the transfer rate is dependent on base separation [ 59 ].…”

Section: Electron Transfer Enhancement By Ruthenium-nucleic Acid Cmentioning

confidence: 99%

Applications of Ruthenium Complexes Covalently Linked to Nucleic Acid Derivatives

et al. 2018

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Oligonucleotides are biopolymers that can be easily modified at various locations. Thereby, the attachment of metal complexes to nucleic acid derivatives has emerged as a common pathway to improve the understanding of biological processes or to steer oligonucleotides towards novel applications such as electron transfer or the construction of nanomaterials. Among the different metal complexes coupled to oligonucleotides, ruthenium complexes, have been extensively studied due to their remarkable properties. The resulting DNA-ruthenium bioconjugates have already demonstrated their potency in numerous applications. Consequently, this review focuses on the recent synthetic methods developed for the preparation of ruthenium complexes covalently linked to oligonucleotides. In addition, the usefulness of such conjugates will be highlighted and their applications from nanotechnologies to therapeutic purposes will be discussed.

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“…However, previous studies have shown, that oxidation of guanosine by DMAPylinked deoxynucleosides as the built-in electron donor is rather unlikely. [17] After irradiation of duplexes D0_ds, D2_ds and D3_ds, followed by enzymatic digestion and RP-HPLC analysis, reduction of the 5BrdU peak area in relation to the peak area of G is clearly visible, thus indicating debromination of 5BrdU and thereby confirming successful charge transfer. Moreover, as already seen in the fluorescence quenching assay, charge transfer occurs in a distance dependent manner, as Q 5BrdU/G is most significantly reduced for D0_ds, followed by D2_ds and D3_ds in relation to Dbr_ds (Figure 2 B).…”

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confidence: 94%

Reductive Charge Transfer through an RNA Aptamer

Frommer

Müller

2020

Angewandte Chemie

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The transfer of charges through double helical DNA is a very well investigated bioelectric phenomenon. RNA, on the contrary, has been less studied in this regard. The few available data report on charge transfer through RNA duplex structures mainly composed of homonucleotide sequences. In the light of the RNA world scenarios, it is an interesting question, if charge transfer can be coupled with RNA function. Functional RNAs however, contain versatile structural motifs. Therefore, electron transport also through non-Watson-Crick base-paired regions might be required. We here demonstrate distance-dependent reductive charge transfer through RNA duplexes and through the non-Watson-Crick base-paired region of an RNA aptamer.

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Acceleration of Long‐Range Photoinduced Electron Transfer through DNA by Hydroxyquinolines as Artificial Base Pairs

Cited by 9 publications

References 39 publications

Modulation of Excess Electron Transfer through LUMO Gradients in DNA Containing Phenanthrenyl Base Surrogates

Modulation of Excess Electron Transfer through LUMO Gradients in DNA Containing Phenanthrenyl Base Surrogates

Applications of Ruthenium Complexes Covalently Linked to Nucleic Acid Derivatives

Reductive Charge Transfer through an RNA Aptamer

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